MX2015003370A - Ethylene-based polymer compositions, and articles prepared from the same. - Google Patents

Abstract

The invention provides a composition comprising a first composition, wherein the first composition comprises a first ethylene-based polymer and a second ethylene-based polymer, and wherein the first composition has a high load melt index (I21) less than 17, a density greater than, or equal to, 0.952 g/cm3, a molecular weight distribution MWD (conv), defined as the ratio of the weight average molecular weight to the number average molecular weight (Mw (conv)/Mn (conv)), greater than, or equal to, 11; and a viscosity ratio, ŋ(0.01 s-1)/ŋ(100 s-1) at 190°C, greater than, or equal to, 60.

Description

POLYMERIC COMPOSITIONS BASED ON ETHYLENE AND ARTICLES PREPARED FROM THEMSELVES Reference to related requests The present application claims the benefit of US Provisional Application 61/600, 372, filed on September 13, 2012.

Background of the Invention The present invention provides polymer compositions based on ethylene and articles prepared therefrom. The compositions of the following invention are particularly suitable for use in blow molded articles and, in particular, in sealed lid drums and trays.

The previous technique has included polymers with good mechanical properties, but poor processing or improved processing, at the expense of mechanical properties. The trimodal resins have been designed for drums using complex polymerization processes of three reactors. The polymeric compositions are descriin the following references: W02009 / 085922, W02008 / 137722, W02003 / 091 329, US20070213205, US20090306299, US201 000939951, US6604598, EP2105464A1 and EP0533154A1. However, the need remains for new compositions that provide better processability, as well as excellent mechanical properties. These needs have been met in the present invention.

Brief Description of the Invention The present invention provides a composition comprising a first composition, wherein the first composition comprises a first polymer based on ethylene and a second polymer based on ethylene, and in which the first composition comprises a flow index with heavy load ( l2i) less than 17g / 10min, a density greater than or equal to 0.952g / cm3, a conventional Molecular Weight Distribution (DPM (conv)) defined as the ratio of mass average molecular weight to number average molecular weight ( MW (conv) / Mn (conv)), greater than or equal to 11; and a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C greater than or equal to 60.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates the melt strength profiles (REF) of some resins of the invention and comparative resins.

Detailed description of the invention As discussed above, the present invention provides a composition comprising a first composition, wherein the first composition comprises a first polymer based on ethylene and a second polymer based on ethylene, and wherein the first composition has an index of flowability with heavy load (l2) less than 17g / 10min, a density greater than or equal to 0.952g / cm3, a DPM (conv) defined as the ratio of the mass average molecular weight MW, to the average molecular weight in MN number , greater than or equal to 1 1; and a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C greater than or equal to 60.

A composition of the present invention may comprise a combination of two or more embodiments of those descriherein.

The first composition may comprise a combination of two or more embodiments such as those descriherein.

The first ethylene-based polymer can comprise a combination of two or more embodiments as descriherein.

The second ethylene-based polymer may comprise a combination of two or more embodiments as descriherein.

In one embodiment, the first composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C greater than or equal to 65, additionally, greater than or equal to 70.

In one embodiment, the first composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C less than or equal to 1 10, additionally less than or equal to 100.

In one embodiment, the first composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C from 60 to 1 10, additionally, from 60 to 100.

In one embodiment, the first composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C from 65 to 1 10, additionally, from 65 to 100.

In one embodiment, the first composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C from 70 to 1 10, additionally, from 70 to 100.

In one embodiment, the first composition has a viscosity in the molten state (h), at 0.01 s 1 and 190 ° C less than or equal to 200,000 Pa-s, additionally, less than or equal to 195,000 Pa-s.

In one embodiment, the first composition has a melt viscosity (h), at 0.01 s 1 and 190 ° C greater than 120,000 Pa-s, additionally, greater than 130,000 Pa-s.

In one embodiment, the first composition has a melt viscosity (h), at 0.01 s 1 and 190 ° C from 120.00 to 210,000 Pa-s, additionally, from 130,000 to 200,000 Pa-s.

In one embodiment, the first composition has a melt viscosity ratio (h), at 0.01 s 1 and 190 ° C from 120,000 to 200,000 Pa-s, additionally, 130,000 to 195,000 Pa-s.

In one embodiment, the first composition has a ratio 121/15 less than or equal to 25.0, additionally, less than or equal to 24.5, and additionally, less than or equal to 24.0.

In one embodiment, the first composition has a ratio 121/15 greater than or equal to 16.0, additionally, greater than or equal to 18.0 and additionally, greater than or equal to 19.0.

In one embodiment, the first composition has a delta tangent, at 0.01 s 1 and 190 ° C, less than 2.5, additionally, less than 2.3, and additionally, less than 2.0.

In one embodiment, the first composition has a delta tangent, at 0.01 s 1 and 190 ° C, less than 2.3, additionally less than 2.0, and additionally less than 1.8.

In one embodiment, the first composition has a delta tangent, at 0.01 sec 1 and 190 ° C, greater than or equal to 1.1, additionally greater than or equal to 1 .3.

In one embodiment, the first composition has a delta tangent, at 0.01 sec 1 and 190 ° C, greater than or equal to 1.2, additionally greater than or equal to 1.4.

In one embodiment, the first composition has a ratio of tan delta (tan delta to 0.01 s 1) / tan delta to (100 s 1) at 190 ° C, less than or equal to 3.5, additionally, less than or equal to 3.2.

In one embodiment, the first composition has a ratio of tan delta (tan delta to 0.01 s 1) / tan delta to (100 s 1) at 190 ° C, greater than or equal to 2.0, additionally, greater than or equal to 2.2.

In one embodiment, the first composition has a density of 0.952 to 0.958 g / cm3, additionally, of 0.953 to 0.957 g / cm3, additionally, of 0.953 to 0.956 g / cm3 (1 cm3 = 1 cc).

In one embodiment, the first composition has a DPM (conv) greater than or equal to 12, additionally, greater than or equal to 14, additionally, greater than or equal to 16.

In one embodiment, the first composition has a DPM (conv) less than or equal to 30, additionally, less than or equal to 28.

In one embodiment, the first composition has a DPM (conv) from 10 to 30, additionally, from 12 to 28.

In one embodiment, the first composition has an Mz (conv) greater than or equal to 1,000,000 g / mol, additionally, greater than or equal to 1, 100,000 g / mol.

In one embodiment, the first composition has a melting temperature (Tm) greater than 125 ° C and is also greater than 128 ° C, and also greater than or equal to 130 ° C determined by CBD.

In one embodiment, the first composition has a value of vinyls / 1000 C, determined according to ASTM D6248, less than or equal to 0.3, preferably less than or equal to 0.2.

In one embodiment, the first composition has a value of vinyls / 1000 C, determined according to ASTM D6248, less than or equal to 0.30, additionally less than or equal to 0.25, additionally less than or equal to 0.21.

In one embodiment, the first composition has a value of vinyls / 1000 C, determined according to ASTM D6248, greater than or equal to 0.01, additionally greater than or equal to 0.2.

In one embodiment, the first composition has a value of vinyls / 1000 C, determined according to ASTM D6248, less than or equal to 0.3, preferably less than or equal to 0.2.

In one embodiment, the first composition has a value of vinyls / 1000 C, determined according to ASTM D6248, less than or equal to 0.30, additionally less than or equal to 0.25, additionally less than or equal to 0.21.

In one embodiment, the first composition has a value of vinyls / 1000 C, determined according to ASTM D6248, greater than or equal to 0.01, additionally greater than or equal to 0.02.

In one embodiment, the first ethylene-based polymer is an ethylene-based interpolymer. In another embodiment, the first ethylene-based polymer is an ethylene-based copolymer.

In one embodiment, the second ethylene-based polymer is a ethylene-based interpolymer. In another embodiment, the second ethylene-based polymer is an ethylene-based copolymer.

In one embodiment, the second ethylene-based polymer is a polyethylene homopolymer.

In one embodiment, the first ethylene-based polymer is a heterogeneously branched ethylene-based interpolymer, and also a copolymer. The heterogeneously branched interpolymers as known in the art, are typically produced by Ziegler-Natta type catalysis, and contain an inhomogeneous distribution of comonomers between the interpolymer molecules.

In one embodiment, the second ethylene-based polymer is a heterogeneously branched ethylene-based interpolymer, and also a copolymer.

In one embodiment, the first ethylene-based polymer is formed in the presence of at least one catalyst, which comprises at least two catalytic sites.

In one embodiment, the second ethylene-based polymer is formed in the presence of at least one catalyst, which comprises at least two catalytic sites.

In one embodiment, both the first ethylene-based polymer and the second ethylene-based polymer are formed in the presence of at least one catalyst, which comprises at least catalytic.

In one embodiment, the first ethylene-based interpolymer is an ethylene / α-olefin interpolymer, and further an ethylene / α-olefin copolymer. In another embodiment, the α-olefin is selected from the group consisting of α-olefins of 3 to 20 carbon atoms, additionally α-olefin of 3 to 10 carbon atoms. In still another embodiment, the α-olefin is selected from a group consisting of propylene-butene, 1-pentene, 1-hexene, 1-heptene, 1-ketene, 4-methyl-1-pentene, 1 -nonne and 1 -decene, and preferably the group consisting of propylene, 1-butene, 1 -hexene and 1-ketene is selected, and more preferably, the α-olefin is 1 -hexene.

In one embodiment, the second ethylene-based interpolymer is an ethylene / α-olefin interpolymer and further an ethylene / α-olefin copolymer. In another embodiment, the α-olefin is selected from a group consisting of α-olefins of 3 to 20 carbon atoms, additionally α-olefins of 3 to 10 carbon atoms. In still another embodiment, the α-olefin is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-ketene, 4-methyl-1-pentene, 1 -nene and 1 -decene, and preferably the group consisting of propylene, 1-butene, 1 -hexene and 1-ketene is selected, and more preferably, the α-olefin is 1 -hexene.

In one embodiment, the first ethylene-based polymer is present in an amount of 40 to 70% by weight, additionally 50 to 70% by weight, and in addition to 55 to 70% by weight, based on the sum of the weight of the first ethylene-based polymer and the second ethylene-based polymer.

In one embodiment, the second ethylene-based polymer is present in an amount of 30 to 60%, additionally 30 to 50%, and additionally 30 to 45% based on the sum of the weight of the first polymer based on ethylene and the second polymer based on ethylene.

In one embodiment, the first composition comprises more than 90%, additionally more than 95%, and additionally more than 98% by weight of the first polymer based on ethylene and the second polymer based on ethylene, based on the weight of the first composition.

In one embodiment, the composition comprises more than 90%, additionally more than 95%, and additionally 98% by weight of the first polymer based on ethylene and the second polymer based on ethylene, based on the weight of the composition.

In one embodiment, the first composition has an expansion value in the die or matrix (t300 measured at a cutting speed of 300s 1 and 190 ° C) greater than or equal to 18 seconds.

In one embodiment, the first composition has an expansion value in the die or matrix (t1000 measured at a cutting speed of 1000s 1 and 190 ° C) greater than or equal to 6 seconds.

In one embodiment, the composition has an expansion value in the die or matrix (t300 measured at a cutting speed of 300s 1 and 190 ° C) greater than or equal to 18 seconds.

In one embodiment, the composition has an expansion value in the die or matrix (t1000 measured at a cutting speed of 1000s 1 and 190 ° C) greater than or equal to 6 seconds.

In one embodiment, the first composition has a resistance to environmental stress cracking (RAEA F50) greater than or equal to 400 hours, determined according to ASTM D-1693, Method B, in a 10% by volume aqueous solution of IGEPAL CO 630.

In one embodiment, the composition has a value of RAEA F50 greater than or equal to 400 hours determined according to ASTM D-1693, Method B, in a 10% by volume aqueous solution of IGEPAL CO 630.

The present invention also provides an article comprising at least one component formed from a composition of the present invention. In another embodiment, the article is a blow molded article. In another embodiment, the article is an article molded by extrusion by blowing.

An article may comprise a combination of two or more modalities as described herein.

The composition may comprise the combination of two or more embodiments such as those described herein.

The first composition may comprise a combination of two or more embodiments such as those described herein.

The first ethylene-based polymer can comprise a combination of two or more embodiments as described herein.

The second ethylene-based polymer may comprise a combination of two or more embodiments as described herein.

It has been found that the compositions of the invention generally offer a higher melt strength to improve the preform's sag resistance, greater expansion, and a wider molecular weight distribution for easier processing, compared to conventional compositions of the technique. In comparison with unimodal resins, it has been found that the resins of the present invention offer equivalent processing properties or superior mechanical properties, and the option of producing calibrated containers, while at the same time meeting critical performance criteria.

Composition In one embodiment, the composition comprises more than or equal to 90% by weight, addition to the mind greater than or equal to 95% by weight, and more preferably greater than or equal to 98% by weight of the sum of the weight of the first polymer based on ethylene and the second polymer based on ethylene, based on the weight of the composition.

In one embodiment, the composition comprises more than or equal to 90% by weight, more than or equal to 95% by weight, and more than or equal to 98% by weight of the first composition, based on the weight of the composition.

In one embodiment, the composition does not comprise any other polymer, except the first polymer based on ethylene and the second polymer based on ethylene.

In one embodiment, the composition does not comprise any other polymer present in an amount greater than 5% by weight, additionally in an amount greater than 2.5% by weight, based on the weight of the composition, except for the first polymer based of ethylene and the second polymer based on ethylene.

In one embodiment, the composition does not comprise an azide coupling agent.

In one embodiment, the composition has a heavy load index (12) of 5 to 17 g / 10 min, additionally of 6 to 15 g / 10 min.

In one embodiment, the composition has a flow index (15) of 0.1 to 1 g / 10min, additionally 0.2 to 0.8g / 10m / n.

In one embodiment, the composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C, greater than or equal to 65, additionally greater than or equal to 70.

In one embodiment, the composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C, less than or equal to 1 10, additionally less than or equal to 100.

In one embodiment, the composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C, from 60 to 1 10, additionally from 60 to 100.

In one embodiment, the composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C, from 65 to 1 10, additionally from 65 to 100.

In one embodiment, the composition has a viscosity ratio h (0.01 s 1) / h (100 s 1) at 190 ° C, from 70 to 1 10, additionally from 70 to 100.

In one embodiment, the composition has a melt viscosity (h), at 0.01 s 1 and 190 ° C, less than or equal to 200,000 Pa-s, additionally less than or equal to 195,000 Pa-s.

In one embodiment, the composition has a melt viscosity (h), at 0.01 s 1 and 190 ° C, greater than 120,000 Pa-s, additionally greater than 130,000 Pa-s.

In one embodiment, the composition has a melt viscosity (h), at 0.01 s 1 and 190 ° C, from 120.00 to 210,000 Pa-s, additionally, from 130,000 to 200,000 Pa-s.

In one embodiment, the composition has a melt viscosity (h), at 0.01 s 1 and 190 ° C from 120,000 to 200,000 Pa-s, additionally, 130,000 to 195,000 Pa-s.

In one embodiment, the composition has a ratio 121/15 less than or equal to 25.0, additionally less than or equal to 24.5, and additionally less than or equal to 24.0.

In one embodiment, the composition has a ratio 121/15 greater than or equal to 16.0, additionally greater than or equal to 18.0 and additionally greater than or equal to 19.0.

In one embodiment, the composition has a delta tangent, a 0. 01 s 1 and 190 ° C, less than 2.5, additionally less than 2.3, and additionally less than 2.0.

In one embodiment, the composition has a delta tangent, a 0. 01 s 1 and 190 ° C, less than 2.3, additionally less than 2.0, and additionally less than 1.8.

In one embodiment, the composition has a delta tangent, at 0.01 sec 1 and 190 ° C, greater than or equal to 1.1, additionally greater than or equal to 1.3.

In one embodiment, the composition has a delta tangent, at 0.01 sec 1 and 190 ° C, greater than or equal to 1.2, additionally greater than or equal to 1.4.

In one embodiment, the composition has a ratio of tan delta (tan delta to 0.01 s 1) / tan delta to (100 s 1) at 190 ° C, less than or equal to 3.5, additionally less than or equal to 3.2.

In one embodiment, the composition has a ratio of tan delta (tan delta to 0.01 s 1) / tan delta to (100 s 1) at 190 ° C, greater than or equal to 2.0, additionally greater than or equal to 2.2.

In one embodiment, the composition has a density of 0.952 to 0.958 g / cm3, additionally 0.953 to 0.957 g / cm3, additionally 0.953 to 0.956 g / cm3 (1 cm3 = 1 cc).

In one embodiment, the composition has a DPM (conv) greater than or equal to 12, additionally greater than or equal to 14, and additionally greater than or equal to 16.

In one embodiment, the composition has a DPM (conv) less than or equal to 30, additionally less than or equal to 28.

In one embodiment, the composition has a DPM (conv) of 10 to 30, additionally of 12 to 28.

In one embodiment, the composition has an Mz (conv) greater than or equal to 1,000,000 g / mol, additionally greater than or equal to 1, 100,000 g / mol.

In one embodiment, the composition has a melting temperature (Tm) greater than 125 ° C and additionally greater than 128 ° C, and additionally greater than or equal to 130 ° C determined by CDB.

The composition may comprise a combination of two or more embodiments such as those described herein.

First composition In one embodiment, the first composition comprises more than or equal to 90% by weight, greater than or equal to 95% by weight, and still additionally greater than or equal to 98% by weight of the sum of the weight of the first polymer based on ethylene to the second ethylene-based polymer, based on the weight of the first composition.

In one embodiment, the first composition does not comprise any other polymer, except the first polymer based on ethylene and the second polymer based on ethylene.

In one embodiment, the first composition does not comprise any other polymer present in an amount greater than 5% by weight, additionally in an amount greater than 2.5% by weight, based on the weight of the first composition, except for the first polymer a base of ethylene and the second polymer based on ethylene.

In one embodiment, the first composition has a heavy load index (l2i) of 5 to 17 g / 10 min, additionally of 6 to 15 g / 1 Omin.

In one embodiment, the first composition has a flow index (15) of 0.1 to 1 g / 10min, additionally 0.2 to 0.8g / 10min.

The first composition may comprise a combination of two or more embodiments such as those described herein.

First ethylene-based polymer In one embodiment, the first ethylene-based polymer has a density less than or equal to 0.955g / cm3, additionally less than or equal to 0.950g / cm3, additionally less than or equal to 0.945g / cm3, and additionally less than or equal to 0.940g / cm3. In another embodiment, the first ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer.

In one embodiment, the first ethylene-based polymer has a density greater than or equal to 0.0915g / cm3, additionally greater than or equal to 0.920g / cm3, additionally greater than or equal to 0.925g / cm3, and even more additionally, greater or equal to 0.930g / cm3, or greater than or equal to 0.935g / cm3. In another embodiment, the first ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer.

In one embodiment, the density of the first ethylene-based polymer is in the range of 0.0915 to 0.955 g / cm3, additionally in the range of 0.920 to 0.950 g / cm3, additionally in the range of 0.925 to 0.950 g / cm3. In another embodiment, the first ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer.

In one embodiment, the density of the first ethylene-based polymer is in the range of 0.0930 to 0.950 g / cm3, additionally in the range of 0.932 to 0.945 g / cm3, additionally in the range of 0.934 to 0.945 g / cm3. In another embodiment, the first ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer.

In one embodiment, the first ethylene-based polymer has a flow rate with heavy load (l2i) less than or equal to 2.0g / 1 Omin, in addition less than or equal to 1.5g / 10min, additionally, less than or equal to 1.0g / 10min, and additionally less than or equal to 0.8g / 10min . In another embodiment, the first ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer.

In one embodiment, the first ethylene-based polymer has a melt index (12i) greater than or equal to 0.1 g / 10min, additionally greater than or equal to 0.2g / 10min, additionally, greater than or equal to 0.3g / 10min, and additionally greater than or equal to 0.4g / 10min. In another embodiment, the first ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer.

In one embodiment, the first ethylene-based polymer has a higher molecular weight than the second ethylene-based polymer, determined by the polymerization conditions of each component, the flow index, CPG methods (molecular weights and / or weights). average molecular weight) and / or other methods known in the art.

In one embodiment, the first ethylene-based polymer has a molecular weight distribution (Mw / Mn) greater than 3, additionally greater than 3.5 and still further greater than 3.8, determined by conventional CPG.

In one embodiment, the first ethylene-based polymer is an ethylene / α-olefin interpolymer, and also an ethylene / α-olefin copolymer. In a preferred embodiment, the α-olefin is an α- olefin of 3 to 20 carbon atoms, additionally an α-olefin of 3 to 10 carbon atoms, additionally an α-olefin of 4 to 10 carbon atoms, additionally an α-olefin of 4 to 8 carbon atoms, and additionally an α-olefin of 6 to 8 carbon atoms. Preferred α-olefins include 1 -hexene and 1-ketene, preferably 1 -hexene.

In one embodiment, the first ethylene-based interpolymer is an ethylene / 1 -hexene interpolymer.

The first ethylene-based polymer can comprise a combination of two or more embodiments as described herein. Second Ethylene-based Polymer In one embodiment, the second ethylene-based polymer has a density greater than or equal to 0.955g / cm3, additionally greater than or equal to 0.960g / cm3, additionally, greater than or equal to 0.965g / cm3. In another embodiment, the second ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer. In another embodiment, the second ethylene-based polymer is a polyethylene homopolymer.

In one embodiment, the second ethylene based polymer has a density less than or equal to 0.980g / cm3, additionally less than or equal to 0.975g / cm3. In another embodiment, the second ethylene-based polymer is an ethylene-based interpolymer, and preferably an ethylene-based copolymer. In another embodiment, the second ethylene-based polymer is a polyethylene homopolymer.

In one embodiment, the second ethylene-based polymer has a density of 0.960 to 0.980g / cm3, additionally of 0.965 to 0.975g / cm3. In another embodiment, the second ethylene-based polymer is an ethylene-based interpolymer, and also an ethylene-based copolymer. In another embodiment, the second ethylene-based polymer is a polyethylene homopolymer.

In one embodiment, the second ethylene-based polymer is an ethylene / α-olefin interpolymer, and also an ethylene / α-olefin copolymer. In a preferred embodiment, the α-olefin is an α-olefin of 3 to 20 carbon atoms, additionally an α-olefin of 0 3 to 10 carbon atoms, additionally an α-olefin of 4 to 8 carbon atoms, and additionally an α-olefin of 6 to 8 atoms * of carbon. Especially preferred a-olefins include 1-hexene and 1-ketene, preferably 1 -hexene.

In one embodiment, the second ethylene-based polymer is an ethylene / 1 -hexene copolymer.

In another embodiment, the second ethylene-based polymer is a polyethylene homopolymer.

The second ethylene-based polymer may comprise a combination of two or more embodiments as described herein. 0 Additives The compositions of the present invention may contain one or more additives. The additives include, but are not limited to, processing aids and neutralizers, UV stabilizing agents, agents for decomposing hydroperoxide, agents for collecting 5 alkyl radicals, hindered amine stabilizing agents, multifunctional stabilizers, phosphites, antioxidants, process stabilizers, metal deactivators, additives to improve oxidative or chlorine resistance, pigments or dyes, nucleating agents, stearates, fatty acids, fluoroelastomers, fillers, and combinations thereof.

Manufactured Items The compositions of the present invention can be used for the manufacture of shaped articles, one or more components of a shaped article. Such articles can be single-layer or multi-layer, which typically are obtained by suitable known conversion techniques, heat application, pressure, or a combination thereof to obtain the desired article. Suitable conversion techniques include, for example, extrusion blowing molding, blow molding, blow molding, injection molding, stretch blow molding, blow molding and compression molding. , rotomolded, extrusion, pultrusion, calendering and thermoforming. The shaped articles (coformados) provided by the invention include, for example, drums, buckets with a tight lid, drums, bottles, tubes, percolation tapes, and pipes, geomembranes, films, sheets, fibers, profiles and molded articles. Films include, but are not limited to, blown films, cast films, and b100 films.

The compositions according to the present invention, they are particularly suitable for the manufacture of blow molded containers, which have an excellent balance of mechanical properties. In addition, the weight of the container can be reduced while still meeting the performance requirements of the container. This is advantageous to reduce the cost of the container, as well as to reduce the waste material that is sent to the landfill dumps.

DEFINITIONS Unless otherwise stated, implied by the context, or used in the technique, all parts and percentages are weight-based, and all test methods are the most current until the date of submission. the present description.

The term "composition" as used herein, includes a mixture of materials comprising the composition, as well as the reaction products and decomposition products that are formed from the materials of the composition.

The term "polymer" as used herein, refers to a polymeric compound prepared by the polymerization of monomers, either of the same type or of different types. The generic term "polymer", therefore, embraces the term homopolymer (used to refer to polymers prepared solely from a single type of monomer, with the understanding that trace amounts of impurities may have been incorporated into the polymer structure) and the term "interpolymer" as defined below. As is known in this field, trace amounts of impurities (eg, catalyst residues) may be incorporated into and / or within a polymer.

The term "interpolymer" as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer, therefore, includes copolymers (term used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

The term "olefin-based polymer" as used herein, refers to a polymer comprising, in polymerized form, a majority of olefin monomer, (eg, ethylene or propylene, based on the weight of the polymer) , and optionally may comprise one or more comonomers.

The term "ethylene-based interpolymer" as used herein, refers to an interpolymer comprising, in polymerized form, a majority of ethylene monomer, (based on the weight of the interpolymer), and at least one comonomer.

The term "ethylene / α-olefin interpolymer" as used herein, refers to an interpolymer comprising, in polymerized form, a majority of ethylene monomer (based on the weight of the intrepolymer) and at least one α-olefin.

The term "ethylene / α-olefin copolymer" as used herein, refers to a copolymer comprising polymerized, a majority of ethylene monomer (based on the weight of the copolymer) and an α-olefin, as the only two types of monomers.

The terms "blend" or "polymer blend" as used herein, refer to a mixture or combination of two or more polymers. Such a mixture can be miscible or not. The mixture may or may not be separated in phases. Such a mixture may or may not contain one or more domain configurations, determined from electron transmission microscopy, light scattering, X-ray scattering, and other methods known in the art.

The term "polyethylene homopolymer" and similar terms, as used herein, refer to a polymer polymerized in a reactor, in the presence of ethylene, and in which fresh comonomer is not fed into the reactor. The term "fresh comonomer" as is known in the art, refers to a comonomer power supply located outside the reactor or located outside one or more reactors operating in series or in parallel, and wherein the comonomer is fed into a reactor from this external power source. In the reactor in which the homopolymer is polymerized, very low amounts of comonomer are present if any. The term "typical molar ratio of comonomer to ethylene" is "less than 0.001" to 1 (determined by the minimum concentration of comonomer detected by an in-line gas chromatography instrument at the reactor outlet).

The terms "comprising", "including", "having", and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not it has been specifically described. In order to avoid any doubt, all compositions claimed through the use of the term "comprising" may include any additive, adjuvant or additional compound, whether polymeric or otherwise, unless otherwise stated. In contrast, the term "consisting essentially of" excludes from the scope any subsequent mention of any other component, step or procedure, except those that are not essential for materiality or operability. The term "consisting of" excludes any component, stage or procedure that has not been specifically delineated or listed.

TEST METHODS Density The density of the resin was measured by the Archimedes displacement method, ASTM D792 standard, Method B, in isopropanol. Samples were measured within a period of one hour after molding, after conditioning in the isopropanol bath at 23 ° C, for 8 minutes, until achieving thermal equilibrium, before carrying out the measurement. The samples were compression molded in accordance with ASTM D4703, Annex A, with an initial heating period of 5 minutes at approximately 190 ° C and a cooling rate of 15 ° C / min. for Procedure C. Each specimen was cooled to 45 ° C in the press, with continuous cooling until it "cooled until it could be touched".

Fluidity index by Plastomer Extrusion.

The measurements of the index of Fluency were made with the norm ASTM D1238, conditions at 190 ° C / 2.16kg, conditions at 190 ° C / 5kg and conditions at 190 ° C / 21 6kg, which are known as l5 and 121, respectively (for ethylene-based polymers). The flow rate is inversely proportional to the molecular weight of the polymer. Thus, the larger the molecular weight, the lower the Fluency index, although the relationship is not linear. The Ratio of the Index of Fluency (MFR), is the relation of the index of fluidity (l2i), with respect to the index of fluidity (l2), unless it is specified of another way.

Properties of Modulus of Resistance Flexura I and Secant The stiffness of the resin was characterized by measuring the Flexural Resistance Module at 5% traction and the Secant Module at 1% traction, and a test speed of 0.5 pulses / min (13mm / min), in accordance with the ASTM D790, Method B. The specimens were compression molded in accordance with ASTM D4703 annex 1, with an initial warm-up period of 5 minutes at approximately 190 ° C and a cooling rate of 15 ° C / min for the Procedure C. Each specimen was cooled to 45 ° C in the press, with continuous cooling "until it could be touched".

Traction Properties The tensile strength, elongation resistance, maximum tensile strength, and elongation at break were measured in accordance with ASTM D638, with a test speed of two inches per minute. All measurements were made at 23 ° C, in rigid type IV specimens, which were compression molded in accordance with ASTM D4703, Annex A-1, with an initial warm-up period of 5 minutes at approximately 190 ° C , and a cooling rate of 15 ° C / min, for Procedure C. The specimen was cooled to 45 ° C in the press, with continuous cooling "until it could be touched".

Resistance to Cracking by Environmental Effort (RAEA) Resistance to environmental stress cracking (RAEA) of the resin was measured in accordance with ASTM D1693, Method B, with 10% or 100% by volume IGEPAL CO-630 (supplier, Rhone-Poulenc, NJ) . The specimens were molded in accordance with ASTM D4703, Annex A, with an initial warm-up period of 5 minutes at approximately 190 ° C, and a cooling rate of 15 ° C / min for Procedure C. Each specimen was cooled at 45 ° C in the press, with continuous cooling "until you can touch".

In the RAEA test, the susceptibility of the resin to mechanical failure due to cracking was measured, under conditions of constant stress, and in the presence of a cracking accelerator, such as soap, a wetting agent, and the like.

In accordance with ASTM D1693, Method B, the measurements were carried out on notched samples, in an aqueous solution of IGEPAL CO-630 at 10% by volume, maintained at 50 ° C. 10 samples were evaluated per measurement. The RAEA value of the resin was reported as F50, which is the 50% failure time calculated from the samples, from the probability graph. Differential Scanning Calorimetry (CDB) The melting temperature (Tm) peak, the heat of fusion (AHm), the peak crystallization temperature (Te), and the heat of crystallization (AHc), were generated by a differential scanning calorimeter TA Instruments model Q1000 CDB, equipped with a cooling cooling system (SER) and an automatic sampler. A purge with nitrogen at a flow of 50ml / min was carried out throughout the test. The sample was compressed to form a thin film, using a press at 175 ° C and 1500 psi (10.3MPa) of maximum pressure, for approximately 15 seconds, and then cooled in air to room temperature, at atmospheric pressure. Then, approximately 3 to 10mg of the material was cut on a 6mm diameter disc using a paper punch, weighed to an accuracy of 0.01 mg, placed on a light aluminum tray (approx 50mg), and then it was engargoló.

The thermal behavior of the sample with the following temperature profile was investigated. The sample was rapidly heated to 180 ° C and remained isothermal for 3 minutes, in order to remove any previous thermal history. Afterwards, the sample was cooled to -40 ° C, at a cooling rate of 10 ° C / min, and kept at -40 ° C for 3 minutes. Then, the sample was heated to 150 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves were recorded. The Te and the AHc were determined from the cooling curve, and the Tm and AHm were determined from the second heating curve.

Conventional Gel Permeation Chromatography (CPG conv) The chromatographic system consisted of a Polymer Laboratories model PL-210 or a Polymer Laboratories model PL-220. The column and carousel compartments were operated at 140 ° C. The columns used were 3 mixed-B columns of 10 micras from Polymer Laboratories. The solvent used was 1, 2, 4-trichlorobenzene. The samples were prepared at a concentration of "0.1 grams of polymer in 50 milliliters of solvent". The solvent used to prepare the samples contained 200 ppm of butylated hydroxytoluene (BHT). The samples were prepared by shaking slightly for two hours at 160 ° C. The injection volume used was 100 pL, and the flow rate was 1.0 milliliters / minute.

The CPG column calibration was performed with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures, with less a decade of separation between the individual molecular weights. The standards were purchased from Polymer Laboratories (Shropshire, GB). Polystyrene standards were prepared at "0.025 grams in 50 milliliters of solvent" for molecular weights less than 1000kg / mol. The polystyrene standards were dissolved at 80 ° C with gentle agitation for 30 minutes. Standard narrow molecular weight mixtures were run first and in order to decrease the higher molecular weight component to minimize degradation. The standard peak molecular weights of polystyrene were converted to molecular weights of polyethylene, using the following equation: Mpolyethylene = A x (Mpolystyrene) 6, where M is the molecular weight, A has a value of 0.431 and B is equal to 1. 0 Polyethylene equivalent molecular weight calculations were performed using VISCOTEK software TriSEC version 3.0 Reology Each sample was compression molded to form a disc to measure rheology. The discs were prepared by compressing the samples to form "3.0 mm thick" plates and subsequently cutting into "25 mm diameter" discs.The compression molding procedure was as follows: 350 ° F (177 ° C) per 5 minutes, at 1500psi (10.3 MPa), under protection with N2 purge, then the material was transferred to an oven at room temperature, with N2 purge until the sample plate solidified and then the plate was removed from the mold.

The rheology of the resin was measured in an ARES-model rheometer LS of TA Instruments. The ARES is a stress-controlled rheometer. A rotary actuator (servomotor) applies a shear deformation in the form of tension in a sample. In response, the sample generates a moment, which is measured by the transducer. Tension and momentum are used to calculate dynamic mechanical properties, such as modulus and viscosity. The viscoelastic properties of the sample are measured in the molten state, using a parallel plate of "25mm diameter" set at 190 ° C and as a function of the frequency variation (range 500s 1 to 0.01 s 1). A small constant tension (5%) was applied to ensure that the measurement was in the linear viscoelastic region. The storage modulus (G '), the loss modulus (G "), the tan delta (G" / G') and the complex viscosity (eta *) of the resin were determined using the Rheometrics Orchestator software (v. 6.5.8). Structural Characterization The content of vinyls / 1000C and vinyls trans / 1000C was determined in accordance with ASTM D6248; and the content of methyl groups / 1000C in accordance with ASTM D2238.

Method of Expansion in the Die or Matrix The die expansion test or matrix of the extruded material was used to evaluate the average expansion of a polymer strip exiting the die of an extruder, in a time range representative of a manufacturing process, such as a molding process by blowing. A polymer strip was produced by a piston-driven capillary rheometer (Góttfert 2003, equipped with a barrel of "12mm in diameter" and a circular die of "I mm in diameter" of 10 mm in length, with an entrance angle of 90 °) at cutting rates of 300s 1 or 1000s 1, and at a temperature of 190 ° C. The volumetric flow rate remained constant. The strip was cut at a distance of 4 cm from the die exit and the cutter was switched on. When the strip reached a total of 27cm (ie an incremental length of 23cm after the cutter had been started), the cutter was stopped. High expansion materials produce a thicker extrudate whose length grows more slowly than that of materials that expand less. The time recorded for the strip to reach the incremental length of "23cm" is related to the expansion with the die or matrix. The review was repeated 5 times, to take into account the variability and the average result was reported. The expansion in the die or matrix of the extruded material was reported in the present as time, ti 000 seconds, required for the extruded material to cover the distance of 23cm when it was extruded at a cutting rate of 1000s 1 and the time t30o seconds , when the cutting rate of the extrusion was 300s 1 EXPERIMENTAL PART The following examples are presented to illustrate the present invention, and not to limit it. Relations, parts and percentages are given by weight, unless otherwise indicated.

The catalyst was prepared using the equipment and methods described in US Pat. No. 6,982,237 (which incorporated herein by reference). See also international patent publication WO 2009/085922. The catalyst was prepared in accordance with the following formulation shown in Table 1. The catalyst formulation was spray-dried - see Table 1 below.

Table 1: Catalyst formulation Representative Chlorination The spray-dried catalyst precursor was subsequently chlorinated with ethylaluminum sesquichloride (SCEA) as a chlorinating agent, a CI / OEth auxiliary was added in a molar ratio of about 2.0. A 6-liter glass flask equipped with heating jacket and helical agitator was used in the chlorination reaction. Some pressure was generated by gases that were released during the chlorination cap, due to the reaction of the residual alcohol with the alkyl groups of ethylaluminum sesquichloride.

The mixing tank was charged with 2500 grams of hexane. The temperature control was set at 20 ° C. The agitator started at 50% of its maximum speed. The precursor powder (600-700 grams), then, was added to the reactor, and the mixture was stirred for 30 minutes. minutes to disperse the precursor. Then, the SCEA solution (available at 30% by weight in hexane) was loaded into the alkylation system. The pressure controller was adjusted to 2 psig. The SCEA solution was loaded in increments of 100 grams, waiting for 10 to 15 minutes to observe gas evolution. The addition was stopped if excessive foaming occurred, or if the temperature increased above 45 ° C. The addition was summarized after the foaming had ceased and after the temperature had dropped below 45 ° C. The temperature control point was increased to 50 ° C and the slurry was stirred for 60 minutes after reaching that temperature. After 60 minutes of agitation, the agitator was turned off, to allow the slurry to settle. A dip tube for decanting was inserted into the tank through a gasket. The tank pressure was increased to approximately 10psig and the supernatant liquid was removed by suction.

Charge (2500 grams) of isopentane in the tank and the slurry was stirred for 30 minutes. The temperature control was set at 35 ° C. The agitator was turned off to allow the slurry to settle. A dip tube for decanting was inserted into the tank through a gasket. The tank pressure was increased to approximately 10psig and the supernatant liquid was removed by suction. The process of isopentane addition, stirring and decanting was subsequently repeated. After the second washing and decanting, "2500 cc "of dehydrated HB-380 mineral oil to the tank, and the mixture was slowly stirred just enough to start mixing the slurry. The temperature of the jacket was raised to 45 ° C and the system was subjected to vacuum to remove the residual isopentane. As the material was formed, the vacuum was regulated to prevent any carry. When the internal temperature began to rise to more than 35 ° C, the vacuum was discontinued. Then, the catalyst was placed in a sample container and prepared for use.

The continuity additive was a mixture of commercially available aluminum distearate and AS-990 (ethoxylated stearylamine), dispersed in mineral oil at a 10% loading of each component. The mineral oil HB-380 is the one that is typically used, but any mineral oil with high viscosity, dry and free of oxygen, can be used as a dispersible agent.

The polymerizations were carried out in a pilot scale reactor, in the manner described in US Pat. No. 6,187,866, which is incorporated herein by reference. The catalyst was fed only in the first reactor. Cocatalyst and Continuity Additive (CA) were also fed separately to the first reactor. The addition of the AC was carried out at a bed height of approximately 30 centimeters (1 foot) above the catalyst feed point, however, this is not a critical feature of the polymerization process. The AC feed rate was maintained at a value of approximately 5 to 50 ppm based on the rate of polymer production, at a enough to control the formation of sheets.

Representative polymerizations, as shown in the tables presented below, were not deliberately added comonomer to the second reactor; however, small amounts (equivalent to those dissolved in the polymer, with a molar ratio of comonomer to ethylene less than 0.001 / 1 (according to the gas chromatograph reading in line in the reactor)) are carried to the second reactor. There was an optional cocatalyst feed in this second reactor. The reaction conditions used to produce these samples are presented in Tables 2 and 3.

The properties of the resin are shown in Tables 4 to 9. In Figure 1, an overlay of the melt strength data is shown. The resins of the present invention are especially suitable for manufacturing blow molded containers such as drums.

It has been found that the compositions of the present invention offer generally improved processing, higher melt strength to improve the preform warpage resistance, greater expansion and a broad molecular weight distribution, for easy processing, in comparison with comparative bimodal resins (see Comparative Examples A and B). In comparison with the unimodal resins (see Comparative Examples C-E), which are typically catalyzed with chromium, it has been found that the resins of the present invention offer equivalent processing, superior mechanical properties and the option of producing calibrated containers, while still meeting the critical performance criteria. The unique combination of characteristics of the compositions of the present invention provides the improved processing and improved resin properties mentioned above, over other compositions of the art.

Table 2: Reactor conditions * ppm based on the amount of polymer produced ** ppm based on the amount of polymer produced ***% by weight of the high molecular weight component, based on the total polymer produced Table 3: Reactor conditions * ppm based on the amount of polymer produced ** ppm based on the amount of polymer produced ***% by weight of the high molecular weight component, based on the total polymer produced Table 4: Properties of the Resin Table 5: Properties of Resin Table 6: Properties of the Resin Table 7: Properties of the Resin a) Unimodal ethylene / hexene (EH) copolymer, Cr b) Ineos K44-1 1 -128 catalyst c) Chevron HXM 50100 Table 8: Properties of the Resin Table 9: Properties of the Resin

Claims (13)

1. CLAIMS 1. A composition characterized in that it comprises a first composition, wherein the first composition comprises a first polymer based on ethylene and a second polymer based on ethylene, and in which the first composition comprises a flow index with a heavy load (121) lower of 17, a density greater than or equal to 0.952 g / cm3, a molecular weight distribution DPM (conventional) defined as the ratio of mass average molecular weight to number average molecular weight (Mw (conv) / Mn (conv. )), greater than or equal to 1 1; and a viscosity ratio h (0.01 s-1) / q (100 s-1) at 190 ° C, greater than or equal to 60. 2. The composition according to claim 1, characterized in that the first composition has a melt viscosity (h), at 0.01 s 1 (190 ° C), less than 200,000 Pa-s. 3. The composition according to any of the preceding claims, characterized in that the first composition has a ratio l2 / less than or equal to 25.0. 4. The composition according to any of the preceding claims, characterized in that the first composition has a density of 0.952 to 0.958 g / cm3. 5. The composition according to any of the preceding claims, characterized in that the first composition has a Delta tangent, at 0.01 s 1 (190 ° C) lower than 2. 3. 6. The composition according to any of the preceding claims, characterized in that the first composition has a Delta tangent, at 100s 1 (190 ° C), less than or equal to 2.0. 7. The composition according to any of the preceding claims, characterized in that the first composition has a (conventional) DPM greater than or equal to 16. 8. The composition according to any of the preceding claims, characterized in that the first composition has a (conventional) DPM less than or equal to 28. 9. The composition according to any of the preceding claims, characterized in that the first ethylene-based polymer is an ethylene-based interpolymer. 10. The composition according to any of the preceding claims, characterized in that the composition has a resistance to environmental stress cracking F50 greater than 400 hours, determined in accordance with ASTM D1693, Method B, in 10% aqueous IGEPAL. eleven . The composition according to any of the preceding claims, characterized in that the first composition has a value of "vinyl / 1000C" determined in accordance with ASTM D6248, less than or equal to 0.3. 12. The composition according to any of the preceding claims, characterized in that the composition has a value of "vinyls / 1000C" determined in accordance with the ASTM D6248 standard, less than or equal to 0.3. 13. An article characterized in that it comprises at least one component formed from the composition according to any of the preceding claims.